Process of treating hydrocarbon vapors with zinc chloride



Patented Feb. 15, 1938 i t UNITED STATES PATENT OFFICE v raooEss F TREATING HYDROCARBON' vnrons WITH zmo omloamn Franklin E. Kimball, Los Angeles, Calif.

No Drawing. Application July 21, 1936,

Serial No. 91,788.

9 Claims. (01. 196-36) This invention relates to processes ofrtreating carbon liquid and by withdrawing the condensed hydrocarbon vapors with zinc chloride and has gum-containing hydrocarbon liquid. for its object to render more expeditious. and I Willhereinbelow describea preferred embodicheaper the application of said processes by emment of my improvements in processes of treatploying the use ofa fused maintained treatinging hydrocarbon vapors. with fused zinc chlo- 5 mixture containing sufiicient'zinc chloride to preride. The description is an example of an illusvent separation of ammonium chloride and sufiltration portraying my improvements. It is to cient ammonium chloride to prevent separation of be understood that my invention is not limited zinc chloride atatemperature between 355- degrees nor restricted to the employment of the use of 10 Fahrenheit andzinc chloride melting-temperathe precise mixtures, concentrations, quantities, l0, ture. proportions, pressures nor temperatures whose use Considerably above 355 degrees Fahrenheit apare employed in the operation of such an illusproximately the'same degree of heat melts zinc trative process as is thus hereinbelow described chlorideas decomposes ammonium chloride. Amas being a practi al ex mp of an application l5 monium. chloride does not melt with heat but it whichv portrays my improvements. decomposes with heat. 7 Solid ammonium chloride Incthe application of such an illustrative procexists only in the form, of needle-like crystals ess', mineral oil may be continuously supplied to which pack down and form the interstices too a suiab-le heater and continuously cracked under small to conduct the hydrocarbon vapors through pressure by processes well-known to those skilled 2Q; the ammonium chloride with a practical velocity intheart of manufacturing gasoline. From sul- At a temperature of 355 degrees Fahrenheit a. phur be rin ils, hy 1' arbon v p rs n n n mixture of three parts of zinc chloride and, one hydrogensulphide may be Continuously formedpart of ammonium chloride liquefies. Theijvapors may then be continuously separated I pass hydrocarbon vapors containing hydro fr mlr nvap rize res u Th v p r y n gen sulphide and gum-forming vapors at a tem be .cohtinuously partially dephlegmated. At a 25 perature between355 and 487 degrees Fahrenheit pressure between 50 and 100 pounds per square beneath the surface'of a fused maintained treatinch gage pressure, the vapors may then be coning-mixture containing approximately three parts tinuously further partia ly Cooled and Partially of zinc chloride to prevent, separation of amoondensedto such a d e that the Vapors may monium chloride and one part of ammonium be continuously Withd aw from e dephlegma- 30 chloride to prevent separationof zinc chloride, tionyessel at a te p e b ween 3 a d 487 supply to the treating-mixture a fused mixture degrees Fahrenheit. of chlorides ofzinc and'ammonimn, separate and The pre ures of the application t e t eatwithdrawthe vaporsfrom the treati 'ig-mixture, ment'of the hydro a n Vapors y be V withdraw from the treating-mixture a fused mixtrolled by employin the use of suitable pressure 5 tule of chlorides of zinc and ammonium, containe a s s c as Howell-known to those skilled ing products of reaction, supply ammonia. tothe in the a t of treat hyd a n vapo s. Prio withdrawn vapors, pass the ammonical vapors tothe' nt y of t e vapors into the primary bubbeneath t urface f ai t i u o ble-tower, the pressure may he stepped down from 4:0 solutionof calcium chlorida'fsupplyfto the aque the pressure 50 to 100 pounds per Square 40 ous solution of calcium chloride Water and'calinchgagopressure, for ihemaliing of a subjecfifm cium chloride, separate and withdraw the vapors of the q s to polymenza'tlqn, treatment whue from the aqueous solution of calcium chloride and theynexlst in" superheated condltlon at pressure withdraw from the aqueoussol'ution of calcium bet-Ween 10 and 15 pounds per.square Inch gage chloride water and calcium chloride admixed s re. Therqupon polymenzed products may S d minim h dr 0 rb be readily held in the vapor phase because the W c en 6 gu on g y 0 on temperature is still yet above the temperature of hqmd' I remove m' Vapors p their condensation underthe pressure whose use 9 P Vapors y effectntg catalytic poly is being employed in making the application of menza'tlon of t gum'ffJrmmg Vapor? to m the treatment. Again, subsequently to the exit 50 gums, Partlany coohng and partlally of the vapors from the primary bubble-tower, the densing the hyrocarbon Vapors a conpress ure may be stepped down to a pressure he... densed gum-containing hydrocarbon qu d, y tween 5'and 10 pounds per square inch gage separating nd With r wing he ydr arb n va pressurefor the making of a subjection of the pors from'th'e condensed gum-containing hydrovapors a subsequent treatment for removing 55 reaction products from the vapors with a secondary bubble-tower.

At the temperature between 355 and 487 degrees Fahrenheit and the pressure between 10 and 15 pounds per square inch gage pressure, the withdrawn hydrocarbon vapors may then be continuously passed into the bottom of a suitable primary bubble-tower and may be continuously withdrawn from it at the top thereof. A fused mixture of one part of ammonium chloride and three parts of zinc chloride may then be continuously passed into the top of the primary bubble-tower and may be continuously withdrawn from it at the bottom thereof. Within the primary bubble-tower the vapors are brought into contact with the primary treating-mixture by bubbling therethrough in a series of superimposed pans such as are well-known to those skilled in the art of treating hydrocarbon vapors. The vapors, from off of the top of each pan below, pass into the pan above at a point beneath the surface of the liquid therein. The treating-mixture, from off of the top of each pan above, passes into the pan below at a point beneath the surface of the liquid therein. Thereupon the vapors become desiccated by the lower pans.

The treating of the hydrocarbon vapors in the primary bubble-tower may be controlled by manipulations of the amounts of ammonium chloride and of zinc chloride being passed into the top. It is aimed to supply one pound of ammonium chloride and three pounds of zinc chloride for each barrel of gasoline being supplied for treatment. By manipulations of the amounts of the two ingredients of the fused treating-mixture being supplied to the top of the primary bubbletower, the resulting composition of the treatingmixture which is being withdrawn from the bottom of the primary bubble-tower is thereby carefully maintained at a proportion of approximately 25% of ammonium chloride to 75% of zinc chloride. The temperature of the treating of the vapors in the primary bubble-tower may be controlled by manipulations of the amounts and temperatures of the vapors and treating-mixtures being supplied. Thereby, the temperature of the treating-mixture being withdrawn from the bottom of the primary bubble-tower may be carefully maintained at a temperature between 355 and 487 degrees Fahrenheit.

The primary bubble-tower may be constructed of acid-proof materials such as are well-known to those skilled in the art of treating hydrocarbon vapors with zinc chloride.

Gaseous ammonia may then be supplied to the hydrocarbon vapors which have been withdrawn from the primary bubble-tower. Suificient quantities may be supplied to render the vapors slightly ammoniacal.

The ammoniacal hydrocarbon vapors may then be continuously supplied to the bottom of the secondary bubble-tower and continuously withdrawn from it at the top thereof. Aqueous solutions of calcium chloride may then be continuously passed into the top of the said secondary bubble-tower and may be continuously withdrawn from it at the bottom thereof. Within the secondary bubble-tower the vapors may be brought into contact with the aqueous calcium chloride solution by bubbling therethrough in a series of superimposed pans such as are wellknown to those skilled in the art of treating hydrocarbon vapors. The vapors, from off of the top of each pan below, pass into the pan above at a point beneath the surface of the liquid therein. The calcium chloride solution, from off of the top of each pan above, passes into the pan below at a point beneath the surface of the liquid therein. The calcium chloride solution partially cools and partially condenses the vapors thereby forming hydrocarbon liquid containing gums. The vapors generate steam from the aqueous calcium chloride solution thereby facilitating the maintaining of the gasoline hydrocarbons in the vapor phase. The calcium chloride solution also extracts ammonium chloride from the vapors. The condensed hydrocarbon liquid also extracts from the vapors gums that are resultant of zinc chloride catalysis in the primary treatment. Both liquids may be continuously withdrawn from the bottom of the secondary bubbletower.

The treating of the hydrocarbon vapors in the secondary bubble-tower may be controlled by manipulations of the amounts of the ingredients of the solutions that are being supplied to the top of the secondary bubble-tower. It is aimed to supply approximately twenty pounds of calcium chloride in aqueous solution for each barrel of gasoline that is being supplied for treatment. This is in order to flush away adequately the condensing hydrocarbon liquid. Additional amounts of water may also be supplied in the calcium chloride solution in such quantities as are suflicient to ofiset such amounts of water as may be vaporized in the application of the treatment. By the manipulations of the amounts of both ingredients of the solutions being supplied to the top of the secondary bubble-tower, the resulting composition of the aqueous calcium chloride solution which is being withdrawn from the bottom of the secondary bubble-tower may be carefully maintained within the proportions of 35 to 45 per cent of water and to 60 per cent of calcium chloride. The temperature of this exit flow of calcium chloride solution may also be carefully maintained at a temperature between 275 and 325 degrees Fahrenheit by means of manipulations of the temperatures and pressures of the vapors which may be supplied for a subjection to an aqueous calcium chloride treatment.

The withdrawn hydrocarbon vapors from off of the top of the secondary bubble-tower may then be continuously cooled and condensed thereby forming gasoline.

The condensed gasoline may then be further treated with fifty degree Baum sulphuric acid, an aqueous solution of caustic soda and an aqueous solution of sodium plumbite by processes wellknown to those skilled in the art of manufacturing gasoline from sulphur bearing mineral oil.

Although I have hereinabove shown and described only one process of refining gasoline embodying my invention, it is to be understood that various changes and modifications may be made in making the application of my improvements in processes of treating hydrocarbon vapors without departing from the spirit of the invention and the spirit and scope of the appended claims.

I claim:

1. In the refining of hydrocarbon oils, at a temperature below zinc chloride fusion-temperature the step which comprises treating the oil in the vapor phase, at a temperature above 355 degrees Fahrenheit, with a fused maintained treating-mixture containing approximately one part of ammonium chloride to prevent separation of zinc chloride and three parts of zinc chloride to prevent separation of ammonium chloride.

2. In the refining of hydrocarbon oils, at a temperature'below zinc chloride fusion-temperature, the step which comprises treating the oil in the vapor phase, at a temperature above 355 degrees Fahrenheit, with a fused maintained treating mixture containing suflicient' ammonium chloride to prevent separation of zinc chloride and sufficient zinc chloride to prevent separation of ammonium chloride.

3. In the refining of hydrocarbon vapors, at a ing sufficient ammonium chloride to prevent S61)? aration of 'zinc chloride and suflicient-zinc chloride to prevent separation of ammonium ch10- mixture a fused mixture of chlorides of zinc and ammonium containing products of reaction, partially cooling and partially-condensing the withdrawn vapors, separating and withdrawing the partially cooled vapors from the condensed hydrocarbon liquid and withdrawing the condensed hydrocarbon liquid.

5. A process comprising passing hydrocarbon vapors containing gum-forming vapors at a tem'- perature between 355 and 487 degrees Fahrenheit beneath the surface of a fused maintained treating-mixture containing approximately three parts.

of zinc chloride to prevent separation of ammonium chloride and one part of ammonium chloride to prevent separation of zinc chloride, supplying to the treating-mixture a fused mixture of chlorides of zinc and ammonium, separating and withdrawing the vapors from the treating-mixture,

withdrawing from the treating-mixture a fused mixture of chlorides of zinc'and ammonium containing products of reaction, partially cooling and partially condensing the withdrawn vapors, separating and withdrawing the partially cooled vapors from the condensed gum-containing hydrocarbon liquid and withdrawing the condensed gum-containing hydrocarbon liquid.

6. A process comprising passing hydrocarbon vapors containing hydrogen sulphide and gumforming vapors at a temperature between 355 and 487 degrees Fahrenheit beneath the surface of a fused maintained treating-mixture containing approximately three parts of zinc chloride to prevent separation of ammonium chloride and one part of ammonium chloride to prevent separation of zinc chloride, supplying to the treating-mixture a fused mixture of chlorides of zinc and ammonium, separating and withdrawing the vapors from the treating-mixture, withdrawing from the treatingmixture a fused mixture of chlorides of zinc and ammonium containing products of reaction, supplying ammonia to the withdrawn vapors, partially cooling and partially condensing the ammoniacal vapors, separating and withdrawing the V partially cooled vapors from the condensed gumcontaining hydrocarbon liquid and withdrawing the cOndensedgum-cOntaining hydrocarbon liquid.

7. A process comprising passing hydrocarbon vapors at a temperature between 355 and 487 de-- grees Fahrenheit beneath the surface of a fused maintained treating-mixture containing approximately three parts of zinc chloride to prevent separation of ammonium chloride and one part of ammonium chloride to prevent separation of zinc chloride, supplying to the treating-mixture a fused mixture of chlorides of zinc and ammonium, separating and Withdrawing the vapors from the treating-mixture, withdrawing from the treatingmixture a fused mixture of chlorides of zinc and ammonium containing products of reaction, passing the withdrawn vapors beneath the surface of a maintained aqueous solution of calcium chloride, supplying to the aqueous solution of calcium chloride Water and calcium chloride, separating and withdrawing the vapors from the aqueous solution of calcium chloride and withdrawing from the aqueous solution of calcium chloride water and calcium chloride admixed with condensed hydrocarbon liquid. 7

8. A process comprising passing hydrocarbon vapors containing gum-forming vapors at a temperature between 355 and 487 degrees Fahrenheit beneath the surface of a fused maintained treat-.

ing-mixture containing approximately three parts of zinc chloride to prevent separation of ammo" nium chloride and one part of ammonium chloride to prevent separation of zinc chloride, supplying to the treating-mixture a fused mixture of chlorides of zinc and ammonium, separating and withdrawing the vapors from the treating-mixture, withdrawing from the treating-mixture a fused mixture of chlorides of zinc and ammonium containing products of reaction, passing the withdrawn vapors beneath the surface of a maintained aqueous solution of calcium chloride, supplying to the aqueous solution of calcium chloride water and calcium chloride, separating and withdrawing the vapors from the aqueous solution of calcium chloride and withdrawing from the aqueous solution of calcium chloride water and calcium chloride admixed with condensed gum-containing hydrocarbon liquid.

v 9. A process comprising passing hydrocarbon vapors containing hydrogen sulphide and gumforming vapors at a temperature between 355 and 487 degrees Fahrenheit beneath the surface of a fused maintained treating-mixture containing approximately three parts of zinc chloride to prevent separation of ammonium chloride and one part of ammonium chloride to prevent separation of zinc chloride, supplying to the treating-mixture fused mixture of chlorides of zinc and ammonium, sep- 7 arating and withdravring the vapors from the treating-mixture, withdrawing from the treatingmixture fused mixture of chlorides of zinc and ammonium containing products of reaction, supplying ammonia to the withdrawn vapors, passing the ammoniacal vapors beneath the surface of a maintained aqueous solution of calcium chloride, supplying to the aqueous solution of calcium chloride water and calcium chloride, separating and withdrawing the vapors from the aqueous solution of calcium chloride and withdrawing from the aqueous solution of calcium chloride water and calcium chloride admixed with condensed gum-containing hydrocarbon liquid.

FRANKLIN E. KIMBALL. 

